Method of separating ethane from hydrocarbon mixtures



Nov. 3, 1953 M. R. CINES 2,657,761

METHOD oF SEPARATING ETHANE FROM HYDROCARBON MIxTuREs Filed June* 12, 195o 2O ETHYLENE \ETHANE ENmcHED sou/ENT ETHYLENE ENFUCHEDy SOLVENT Patented Nov. 3, 1953 METnoDoF sEPARATlNG- FROM HYDRocARBoN Mrx'rUREs R. Cines, Bartlesville, Okla., assignor to lhlllips Delaware etroleum Company, a corporation of Application June 12, 1950, Serial No. 167,611

tion relates to the separation of ethane fromA ethylene using as the preferential solvent for.v ethane one or a mixture of peruoroami'nes having the general formula wherein y, and z areV l) to 4; y

The art of-ab'sorption is 'an old one, its rst use in the petroleumv industry probablyl being lin natural gasoline plants-Where oil was and is used to selectively absorb gasoline from natural gas. The use of absorption as 'a means forwseparating materials has expar'ided to the separation of hydrocarb-ons of differentV degreesr of saturatic'in.v

i. e., paraiiins from -ol'eflns olefins from di'oleuns, parains from aromatics, etc. Y n

Numerous methods have been devised for carrying out absorption processes such as liquidliquid extraction, wherein a liquid component is separated from a mixture of liquids by av liquid solvent, gas-liquid extraction where a component ina gas stream is separated by a liquid absorbent, and the like. It has been foundl during the development of the extraction art that it is almost impossible to predict whether a particular hydrocarbon or hydrocarbon derivative will or will not extract a particular material. Thus, experimentation is the only sure Way of determining whether a particular hydrocarbon` or derivative may be used in av desired separation. It is an object, of this invention .to recover ethane from C2 hydrocarbon streams.

Another object of this invention is the separation of ethane fromv ethylene. y

Another object is to provide a new solvent for ethane in the presence. of ethylene or other Cz hydrocarbons. u Still another Objectis to provide new solvents for ethane in the presence of ethylene compris'- ing the group of periluo'roarnine's`V encompassed by the general formula [CF'3 CF2)` IICFaKCFil'vl [Craft-ira) :JN

wherein y, and zare to 4.

Other objects and advantascsof this invention will be apparent to one skilled in the art from the following discussion.-

I have discovered an improved group of solvents for the separationof ethane'from ethylene or ethane from-Carhydrocarbon streamsrsaid solvents preferentially dissolving the ethane to 2 a degree much greater than that predicted. My invention embodies selectively absorbing ethane from vethylene or Cz hydrocarbon streams utilizing a liquid perfiuoroamine as the preferential solvent for ethane. The process of my invention can be carried out in numerous ways, and I do not intend to be limited by the particular method used. I have found countercurrent extraction to be particularly advantageous in 'the separation of ethane from other C2 hydrocarbons. In such a process the C2 hydrocarbon 4stream is introduced as a gas vto about the midle of an extrac-` tion column. The liquid solvent, such as heptacosailuorotri-n-butylamine, is introduced near the top of the column. In this manner the rising' gas contacts the solvent in countercurrent relationship so that the gas leanest in ethane contacts the fresh absorbent. Other methods of operation can also he used, such as intermittent batch opera'tin, etc. y

Inroperating'g my process the contacting means' can be a bubble cap column, packed column, or

vother conventional equipment adaptable to gas'-y liquid or liquid-liquid' extraction, the former generally being preferred. I usually prefer operating temperatures which are relatively l'ovv, but not below the freezing temperature of the solvent, which in the case of heptaccsaiiuorotril n-butylamine is e265 F. Of course, ywhen other amines of the group disclosed are used, this lower temperature limit may vary. Iy also prefer that the temperature should not be above about F., the preferred temperature range generally being from 0 to 100 F. Operating pressuresv can beings toy 30o p. s. i., and such that itis sufficient to maintain the perlluoroamine in liquid phase at the operating temperature used. y n

When the ethane-containing feed is introduced tothe extraction column at or near the middle thereof, and the solvent is introduced' in the erentially dissolves the ethane portion of the rising gas. The ygaseous overhead product thus iS higher in etlll Ctllt than the' feed, and' may be relatively pure', or may be only partially freed of ethane, depending' on the gasz'so'lvent ratio and the eil'i'ciency of the contacting". When theoperating conditions of the absorber so adjusted as to provide amore pure produ y solvent, reaching the bottom of the column, is

heated sufliciently to displace a portion 'of' 'the dissolved ethane which rises in the column and" above, the preferred Arange The" displaces ethylene from the descending absorbent. The perfluoroamine and dissolved gas, which may be relatively pure ethane or a gas of greater` ethane content than the feed, is withdrawn from the column and heated at about atmospheric pressure or reduced pressure, thus flashing the absorbed ethane. The solvent is then cooled and returned to the top of the column to repeat the cycle.

The unpredictability of my solvents bears out the fact that it is impossible to predict to any great extent just what materials will be separated by aparticular solvent. As an example of this, 'it wasfound in experimental work that hepta- Vcosailuorotri -nbutylamine will not separate npentane from pentene-l. I have also found that my perfluoroarine solvents are preferentially se- .lcti've for the unsaturated 04's over the saturated `C4s having the same carbon chain coniiguration, "as compared with a non-select1ve hydrocarbon such as mineral seal oil, which further bears out the fact that selectivity foba ehane over ethylene olvents is unpredic a e. u byoltlle' solvents of the group disclosed' which may be used, in addition to heptacosafluoi otri-nbutylamine, are branched chain periiuoroamines such as nonafluoro-sec-butyl undecafluoi-: pentyl heptaiiuoropropyl am1ne,.b1s(pentauo roethyl) heptafluoroisopropyl amine, pena sicroethyl heptaiiuoro-n-propyl nonaflioio-O-nbutyl amine, nonailuoro-n-butyl hepta t,irllo like propyl heptafluoroisopropyl anime and ed b5; along with the simplelpeiiusinines cov ructural formu a isc mg sfturther understanding of some of the 'mara' aspects of my invention are had by referlrinrgd 2 the attached drawing, in which Figures d. 31 ents are schematic flow diagrams of two emb i alves of my invention. Various addltiona v conventional equipment, necespumps and other this invention, will be a for the practice of agiliar to one skilled in the art, and have beten the drawing for the sake of clari y.

descri tions of the figures provide two Eilhods ofpoperating my process. It is naad-,fiere stood, however, that while theyoaligelrleirosxrimnges of m process, vari ialebfxrilade inyadapting the process to the yilarrilous conditions within the scopeof the inven ion.l Refer now to Figure 1 which is a flow dialgra d oi a single absorbent extraction process uti lin one of the solvents of my invention. A C2 lliy rois carbon stream containing ethane and etby erlilre fed through line I to absorption zone I W it is contacted in the upper portion therelfnlln countercurrent relation with an absorbent o y invention introduced via line I2 at a temperatur of 0 to 100 F. and a pressure of 50 to 300 p. s. i. 0 suitable volume ratio of liquid solvent to lgas 1s in the range of 0.5:1 to 10:1. The ethane 1n the gaseous feed stream is preferentially absorbed as the solvent passes downward. As the enriched absorbent reaches the bottom of the absorption zone, it is heated in a suitable manner, such as by reboiler I3, to a temperature in the range of to 50 F. higher than the absorption temperature, causing displacement of a ethane which rises in the column and in turn displaces absorbed ethylene or other material from the descending absorbent. Rich absorbent is withdrawn from the bottom of the absorption zone through line 2| and is passed therethrough to stripping zone |4, where the pressure is generally reduced to near atmospheric pressure, or as portion of the dissolved l 4 low as 50 mm. of mercury, and the temperature is elevated to 25 to 125 F. above the absorption temperature, but not so high that the vapor pressure of the solvent is excessive; thereby causing desorption of ethane. Suitable means for heating the enriched absorbent is reboiler I6, however, other means well-known to those skilled in the art can be readily used. Desorbed ethane is removed from the top of stripping zone ,I4 .through line I1, while lean absorbent is remoy'ed from the bottom thereof through line |8 and is passed therethrough to cooler I9 where it is re'- duced in temperature to that desired for intro'- duction to the b*absorption zone. Ethyleneand other material, when present, are removed from the top of said absorption zone through line 20. Make-up solvent is added to the system through Y line I5.

Refer now to Figure 2 which is a ow diagram of a dual solvent process for separating ethane from a Cz gas stream. A gas feed stream is passed through line 30 to absorption zone 3|, where it is contacted in countercurrent relation with a solvent of my invention for ethane and a suitable solvent for ethylene, such as nitromethane or acetonitrile, pyridine, methylene chloride, propionaldehyde, acetone, etc. at a temperature in the range of 0 to 100 F. and a pressure of 50 to 300 p. s. i. A suitable volume ratio of combined solvents to gas is in the range of 0.5:1 to 10:1. The absorbent for ethane is introduced near the top of the absorption zone via line 32, while the absorbent for ethylene is introduced to the absorption zone near the bottom thereof through line 33. It is a necessary prerequisite of the solvents that they be substantially immiscible with one another so that separation of the two into phases may be accomplished readily. Maximum miscibility of one solvent in the other should not exceed 5 to l0 liquid volume per cent. The solvent for ethane passes downwardly through the column absorbing ethane from the feed gas as it goes, and is withdrawn at the bottom of the zone through line 34 and is passed to stripping zone 36. Stripping zone 36 is similar to zone I4 in Figure 1, and may be any conventional stripper which ls operated at or near atmospheric pressure, such as atmospheric to 50 mm. of mercury, and slightly elevated temperatures in the range of 25 to 125 F. or above. Ethane is stripped from the enriched absorbent and removed from the stripping zone overhead via line 31. Lean absorbent is removed from the bottom of zone 36 via line 38, and is passed through cooler 39, where its temperature is reduced to that desired for admission to the absorption zone. From the cooler the lean adsorbent is passed through line 32 as previously described, to zone 3|. Absorbent rich in ethylene is withdrawn near the top of zone 3| via. line 4|, and is passed therethrough to stripping zone 42, which is also similar to the stripping zone I4 of Figure l. Ethylene is recovered overhead from the stripping zone via line 43, while the lean absorbent is recovered from the bottom thereof through line 44, being passed therethrough to cooler 46, where its ,temperature is reduced in a manner similar to that of the solvent passing through cooler 39. Unabsorbed extraneous gas is removed from absorption zone 3| via. line 45. Make-up absorbent may be added through lines 41 and 48, depending on which solvent is to be made up.

Obviously, other arrangements may be utilized employing my particularly advantageous solvents,

The data in the above table yield a ratioof solu.- biltx of ethane to. solubility of ethylene in a pernoroamine' of 1,9.. The expectedjratio or 13h65@ S0l11b1tie$ in a substantially non-selective.

hydrocarbon of about' 200`A molecular weight is 1.6, thus providingA` an increase insolubilty ofv nearly per cent.

Numerous advantagesmay be hadv by the practice of my invention. When a mixture of ethaneV andethylene are being separated a relatively pure stream of ethane may be obtained. Or, if economics so dictate, a feed stream may be prepared for pure ethylene production whichV would containa minor portion, of,v ethane. (Such procedure might be quite advantageous in preparing a feed for ethylene polymerization.) This stream can then be treated with an additional portion of one or a mixture of my new solvents to provide pure ethylene. A procedurevsimilar to thismay be car- Idout inan advantageous-manner when other materialsare in the C;4 Vfraction to be separated besides ethane and ethylene. For example, the gasmay be iirsttreatedwith my solvent to remove ethane, then with a` solvent for ethylene to separateit from other impurities.v This same procedure may be also carried out, asdisclosed, in adual solvent processrusing countercurrent flow of immiscible solvents.

' Although this processv has beendescribed and exemplified in terms of its preferred modifications, it is understood that various changesy may be made without departing from the spirit and scope of the disclosure and'of the claims..

I claim:

1. 'I'he separation of ethane from C2 hydrocarbon.; streams; using.A a selective solvent` for ethane characterized bythe formula.

where-x,- y, and a' are 0 Ito 4:

2. The separation of ethaneffrom ethylene by selective absorption utilizing a solvent for ethane characterized by the formula where x, y, and a are 0 to 4.

3. The separation of ethane from ethylene by selective absorption utilizing heptacosafluorotrin-butylamine as the selective solvent for ethane.

4. A method for the selective absorption of ethane from a C2 hydrocarbon stream which comprises contacting a C2 hydrocarbon stream containing ethane in countercurrent flow with a solvent characterized by the formula where y, and z are 0 to 4, said solvent preferentially absorbing ethane, removing ethane enriched solvent and desorbing same, and recovering echanger 'a panty-j -iigher 'registratie tire C2 hydrocarbon stream. v

5. A method for the selective absorption of ethane from a gaseous (la` hydrocarbon stream which comprises contacting a C2 hydrocarbon stream containing ethane in countercu-rrent ow inan extraction zonev with a solvent character-f ized by the formula whereA sv; y. and a are 0v to 4,; said solvent preferentially absorbingiethaneasit passes downwardlythrough said zone,. heating, the enriched. solvent' in the bottom offsaid: zone only sufficiently to desorb a minor portionA of absorbed ethane',V sai'd desorbed ethane displacing' other C2. hydrocarbon in the downwardlymoving solvent,l passing-the remaining` ethane enriched Vsolvent to: a' des'o'rpi tion zone where desorption iscarri'ed outlbyfv heating said. enriched: solvent, recovering'ethaneVv of a purity greater than in. the C2`hydrocarbeit` feed stream, and recycling lean solvent from said' desorption zone to saidextraction zone;-

6. A methodv for the selective absorption of'v ethane from` a mixture ofeth'ane andi ethylene which comprises countercurrently contacting such ay mixture withra solvent selective yfor ethane comprising heptacosau'orotri-n-butylamine i atia temperature above 269113.` and not above-150' F. in an absorption zone, said'solvent:preferenzetially absorbing ethane.v asitl passes downwardly" through said zone; heating the enriched solvent in the bottom of said absorption zone to1a-teml perature inthe rangefof"10to50t F". above-that n in the remainder of `theabsorpti'on zone; thereby desorbing a minor portionlof absorbed' ethane.; passing upwardly through: andi displacing" ethylene: from the downwardly moving solvent; passingthe rich solvent'from the bottomv of vsaid zoneto a desorption zone where it is subjected t'oheat-g. ing and pressure` reductionvto cause desorption of j ethane, recovering ethane from*- said desorption zone of a purity higher than that`in-the-feed`i solvent' tosaid abf-r said desorbed ethane said absorption zone stream, recyclingr desorbed sorption zone, and recoveringethyleneof apurity greater than that of thefeed stream from the topr of said absorption i zone;

7. A methodv for thev selective absorption of ,ethane from a gaseous mixture. of ethane: and' ethylene which., comprises; countercurrently con-` tacting such a mixture-with a solvent selective` for ethane comprising-1heptacosaluorotri-nebuatylamine at a temperature inthe rangevotO tof' F. and a pressure,-in1the-. rangecir 0 tof300f' p..s. i., the ratio'of gasto solvent-being;inthe` range of 0.5 to10'liquid2'volumcsof: solventperf` volume of gas, said solvent; preferentially aber sorbing ethane as` it passes; downwardly through'i said absorption zone, l, heatingy then enriched f 'sol'- vent in the bottom of said absorption zone to a. temperature in the range of 10 to 50 F. above that in the rest of the absorption zone and thereby causing a portion of absorbed ethane to be desorbed, said desorbed ethane passing upwardly through said absorption zone and displacing ethylene from the downwardly moving solvent, passing the rich solvent from the bottom of said zone to a desorption zone where it is subjected to heating to a temperature in the range of 25 to 125 F. above the major absorption zone temperature and pressure reduction in the range of atmospheric to 50 mm. of mercury, recovering ethane from said desorption zone of a purity higher than that in the feed stream, recycling cooled desorbed solvent to said absorption zone, and recovering ethylene of a. purity greater than that of the feed stream from the where z, y, and z are to 4, and a solvent for ethylene which is not more than to 10 volume per cent miscible with the solvent for ethane at the opposite ends of an absorption zone and in countercurrent flow to one another, introducing a hydrocarbon stream containing ethane and ethylene to be separated intermediate the ends of said absorption zone, contacting said hydro- -carbon stream with said solvents at a temperature above the freezing points of both of said ,solvents and not higher than 150 F. and a pres.. .sure in the range of atmospheric to 300 p. s. i., .said solvents preferentially dissolving ethane :and ethylene, removing ethane rich solvent from -one end of said absorption zone and ethylene :rich solvent from the opposite end thereof, pass- 'ing said enriched solvents to separate desorp- :tion zones, desorbing said solvents by pressure ,reduction and heating, recovering desorbed iethane and ethylene from said desorption zones of purities greater than in said feed streams, and recycling desorbed solvents back to their respective ends of said absorption zone.

9. A process according to claim 8 wherein said solvent for ethylene is nitromethane and wherein the solvent for ethane is heptacosafiuorotrin-butylamine.

10. A process according to claim 8 wherein said solvent for ethylene is acetonitrile and wherein the solvent for ethane is heptacosafluorotri-n-butylamine.

11. A method for the selective absorption of ethane and ethylene from a mixture thereof, which comprises introducing a solvent for ethane characterized by the formula where y, and 2 are 0 to 4, and a solvent for ethylene which is not more than 5 to 10 volume per cent miscible with the solvent for ethane at the opposite ends oi' an absorption zone and in countercurrent flow to one another, introducing an ethane-ethylene mixture to be separated intermediate the ends of said absorption zone, contacting said mixture with said solvents at a temperature in the range of 0 to 100 F. and a pressure of 0 to 300 p. s. i., said solvents preferentially dissolving ethane and ethylene, removing ethane rich solvent from one end of said absorption zone and ethylene rich solvent from the opposite end thereof, passing said enriched solvents to separate desorption zones, desorblng said solvents by pressure reduction down to atmospheric to 50 mm. of mercury and heating to a temperature in the range of 25 to 125 F. above the absorption temperatures but below the boiling points of the solvents, recovering desorbed ethane and ethylene from said desorption zones of purities greater than in the feed mixtures, and recycling desorbed solvents to their respective ends of said absorption zone.

12. A process for the separation of ethane from a gaseous mixture containing C2 hydrocarbons which comprises contacting said mixture with nonafluoro-sec butyl undecafluoro 2 pentyl heptauoro-propyl amine as a selective solvent for ethane.

13. A process for the separation of ethane from a gaseous mixture containing Cz hydrocarbons which comprises contacting said mixture with bis (pentauoroethyl) heptarluoroisopropyl amine as a selective solvent for ethane.

14. A process for the separation of ethane from a gaseous mixture containing Cz hydrocarbons which comprises contacting said mixture with pentauoroethyl heptafiuoro-n-propyl nonaiiuoro-sec-butyl amine as a selective solvent for ethane.

15. A process for the separation of ethane from a gaseous mixture containing C2 hydrocarbons which comprises contacting said mixture with nonafluoro-n-butyl heptauoro-n-propyl heptafluoroisopropyl amine as a selective solvent for ethane.

16. A process for the separation of ethane from a gaseous mixture containing C2 hydrocarbons which comprises contacting said mixture with a perfluoroamine selected from the group consisting of nonafluoro-sec-butyl-undecafluoro-Z-pentyl heptauoro-propyl amine, bis (pentafluoroethyl) heptafiuoroisopropyl amine, pentauoroethyl heptauoro-n-propyl nonafluoro-sec-butyl amine and nonafluoro-n-butyl heptaiiuoro-npropyl heptafluoro-isopropyl amine and perfiuoroamines having the general formula [CFMCFQI] [CFz(CF2)y] [CF3(CF2)Z]N wherein y, and z are 0 to 4 as a selective solvent for ethane.

MARTIN R. CINES.

References Cited in the le of this patent UNITED STATES PATENTS Number Name Date 2,395,362 Welling Feb. 19, 1946 FOREIGN PATENTS Number Country Date 583,874 Great Britain Jan. 1, 1947 

16. A PROCESS FOR THE SEPARATION OF ETHANE FROM A GASEOUS MIXTURE CONTAINING C2 HYDROCARBONS WHICH COMPRISES CONTACTING SAID MIXTURE WITH A PERFLUOROAMINE SELECTED FROM THE GROUP CONSISTING OF NONAFLUORO-SEC-BUTYL-UNDECAFLUORO-2-PENTYL HEPTAFLUORO-PROPYL AMINE, BIS (PENTAFLUOROETHYL) HEPTAFLUOROISOPROPYL AMINE, PENTAFLUOROETHYL HEPTAFLUORO-N-PROPYL NONAFLUORO-SEC-BUTYL AMINE AND NONAFLUORO-N-BUTYL HEPTAFLUORO-NPROPYL HEPTAFLUOR-ISOPROPYL AMINE AND PERFLUOROAMINES HAVING THE GENERAL FORMULA 